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Azubuike was born in London, England to Kenneth and Chy Azubuike.[1] Azubuike was raised in Tulsa, Oklahoma.[1] Playing for Victory Christian High School, Azubuike led his team to the state title as a sophomore.[1] He eventually became an All-State selection, averaging 39.1 points and 13.3 rebounds and leading his team to the Class 4A State Championship Game as a senior.[1] He was the top scorer in the state of Oklahoma during his last three seasons of high school, averaging 28.5 points as a sophomore and 38.7 points as a junior.[1] Azubuike finished his prep career with 3,530 points, 89 points short of the all-time state scoring mark.[1]

Considered a four-star recruit by Scout.com, Azubuike was listed as the No. 8 small forward and the No. 34 player in the nation in 2002.[2]

Playing under coach Tubby Smith, Azubuike said that the biggest improvement to his game at Kentucky was the ability to create offense through intense defense.[3] As a junior, Azubuike was named to the All-SEC Second Team by the Associated Press and the league's coaches after leading the team and ranking tenth in the SEC in points per game, averaging 14.7 overall.[1] Azubuike was named to the 2005 SEC All-Tournament Team after averaging 18.0 points in three contests.[1] During his time with the organization, Azubuike helped the Wildcats to earn two Southeastern Conference titles, two SEC Tournament titles, and two NCAA Elite Eight appearances.[1] Azubuike averaged 10.0 points and 3.7 rebounds in 97 career games at the University of Kentucky, shooting a 48.5% field goal average for his college career.[1] While attending the University of Kentucky, Azubuike majored in business marketing.[1]

In April 2005, Azubuike announced his plans to enter the draft after his junior year, signing with agent Joel Bell and ending his college eligibility.[4] In the 2005–06 season, Azubuike averaged 12.6 points, 4.0 rebounds, and 1.5 assists in forty-one games with the Fort Worth Flyers of the NBA's Developmental League.[5] Azubuike played with the Denver Nuggets in the 2006 Toshiba Vegas Summer League, where he averaged 16.4 points and finished tied at tenth in the league in scoring.[5] In August 2006, Azubuike was signed by the Houston Rockets as a free agent, but eventually waived by October.[5] Playing for Fort Worth of the Development League again, Azubuike averaged 5.0 rebounds, 3.2 assists, 1.17 steals, and a league-best 26.0 points in 37.7 minutes per contest playing for the Fort Worth Flyers of the NBA Development League, shooting 51.4% from the field and 48.5% from three-point range over twelve games.[3][6]

Impressed with his play, the Golden State Warriors signed Azubuike on January 2, 2007.[3] Azubuike was the first Gatorade Call-Up of the 2006–07 NBA Development League season, and the 49th player overall to be called up to the NBA since the D-League began play in November 2001.[6] During his second season with Golden State, Azubuike expressed an interest in playing for the British team during the build-up to the 2012 London Olympic Games, but was denied British citizenship under the 1981 British Nationality Act.[7] On July 17, 2008, Azubuike signed an offer sheet with the Los Angeles Clippers for a three-year deal worth $9 million, with Golden State having seven days to match the offer.[8] In the final hour, Golden State matched the offer made by the Clippers on July 24, 2008, allowing Azubuike to remain a Warrior.[9]

On November 17, 2009, it was announced that Azubuike would miss the remainder of the 2009–10 season because of a torn patella tendon.[10]

On March 23, 2012, Azubuike was signed by the Dallas Mavericks. As part of his comeback, he was assigned to the Mavericks' D-League affiliate, the Texas Legends.[13] On April 9, 2012, he was recalled by the Mavericks.[14] On April 20, 2012, Azubuike played in his first NBA game since November 14, 2009, against the Golden State Warriors.[15] On June 28, 2012, during the 2012 NBA Draft, Azubuike was traded to the Cleveland Cavaliers.[16] He was waived by the Cavaliers on October 14, 2012.[17]

Azubuike has three siblings: Nonzo, Nesochi and Adaeze.[1] He is a Christian music fan and enjoys creating his own music.[1] During the 2006–07 season, Azubuike made an appearance on Bay Area hip hop station KMEL and conducted an interview while the station played music which he personally produced.[1] Azubuike is a Christian.[19]

Azubuike has been involved with many humanitarian causes during his time in the NBA. Azubuike accepted a personal invitation from Jakaya Kikwete, the President of Tanzania, to take part in Leon H. Sullivan Summit VIII, a five-day convention held from June 2 to June 6, 2008 in Arusha, Tanzania. The convention brought together many of the world's political and business leaders to focus attention and resources on Africa's economic and social development.[20]